JP2018095758A - Oil and fat composition - Google Patents
Oil and fat composition Download PDFInfo
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- JP2018095758A JP2018095758A JP2016242873A JP2016242873A JP2018095758A JP 2018095758 A JP2018095758 A JP 2018095758A JP 2016242873 A JP2016242873 A JP 2016242873A JP 2016242873 A JP2016242873 A JP 2016242873A JP 2018095758 A JP2018095758 A JP 2018095758A
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- glyceride composition
- clay
- mass
- purified
- glyceride
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- 239000000203 mixture Substances 0.000 title claims abstract description 173
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 146
- 239000004927 clay Substances 0.000 claims abstract description 119
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 claims abstract description 85
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 76
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 43
- 239000000194 fatty acid Substances 0.000 claims abstract description 43
- 229930195729 fatty acid Natural products 0.000 claims abstract description 43
- -1 fatty acid esters Chemical class 0.000 claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 claims abstract description 40
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 38
- 238000004332 deodorization Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 230000001877 deodorizing effect Effects 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 11
- 238000004042 decolorization Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000003672 processing method Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 abstract description 14
- 239000003921 oil Substances 0.000 description 32
- 235000019198 oils Nutrition 0.000 description 32
- 239000010779 crude oil Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003925 fat Substances 0.000 description 14
- 235000019197 fats Nutrition 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 235000019482 Palm oil Nutrition 0.000 description 11
- 239000002540 palm oil Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004061 bleaching Methods 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 125000000466 oxiranyl group Chemical group 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000008159 sesame oil Substances 0.000 description 2
- 235000011803 sesame oil Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- XFGDAPQOKJYPQP-UHFFFAOYSA-N 1-chloropropane-1,2-diol Chemical compound CC(O)C(O)Cl XFGDAPQOKJYPQP-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 150000001982 diacylglycerols Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- TVQGDYNRXLTQAP-UHFFFAOYSA-N ethyl heptanoate Chemical compound CCCCCCC(=O)OCC TVQGDYNRXLTQAP-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 150000004667 medium chain fatty acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002759 monoacylglycerols Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003904 phospholipids Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 235000002378 plant sterols Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010497 wheat germ oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/02—Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/006—Refining fats or fatty oils by extraction
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/04—Refining fats or fatty oils by chemical reaction with acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
- C11B3/14—Refining fats or fatty oils by distillation with the use of indifferent gases or vapours, e.g. steam
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Fats And Perfumes (AREA)
- Edible Oils And Fats (AREA)
Abstract
Description
本発明は、精製グリセリド組成物及び該精製グリセリド組成物の製造方法に関する。 The present invention relates to a purified glyceride composition and a method for producing the purified glyceride composition.
近年、風味や安定性等、油脂の品質を向上させるための試みが種々行われている。油脂の品質の低下には、様々な要素が関係している。例えば、３員環のエーテルであるオキシラン構造は、化学的に不安定であるため反応性に富み、重合等の化学反応を起こしやすいことが知られている。このような化学反応が、油脂の品質の低下を引き起こす可能性がある。 In recent years, various attempts have been made to improve the quality of fats and oils such as flavor and stability. Various factors are related to the deterioration of the quality of fats and oils. For example, it is known that an oxirane structure, which is a three-membered ether, is chemically unstable and therefore has a high reactivity and is likely to cause a chemical reaction such as polymerization. Such a chemical reaction may cause deterioration of the quality of fats and oils.
一部のグリセリド組成物には、かかるオキシラン構造を有するエポキシドの１種であるグリシドールの脂肪酸エステルから誘導される可能性がある３−クロロプロパン−１，２−ジオールの脂肪酸エステルが極微量であるが存在する。３−クロロプロパン−１，２−ジオールは、３−ＭＣＰＤとも呼ばれる。３−クロロプロパン−１，２−ジオールの脂肪酸エステルは、脂肪酸の遊離により、３−クロロプロパン−１，２−ジオールを生じる可能性がある。３−クロロプロパン−１，２−ジオール及びその誘導体が高濃度で存在すると健康に悪影響を及ぼすといわれている。しかし、長年にわたって摂取されてきた植物油等の油脂中に存在する微量の３−クロロプロパン−１，２−ジオールが健康に直ちに悪影響を及ぼすとは考えられず、また、３−クロロプロパン−１，２−ジオールの摂取基準値等は定められていないものの、グリセリド組成物中におけるその存在を可能な限り下げることが求められている。 Some glyceride compositions contain trace amounts of fatty acid esters of 3-chloropropane-1,2-diol that may be derived from fatty acid esters of glycidol, one of the epoxides having such an oxirane structure. Exists. 3-Chloropropane-1,2-diol is also called 3-MCPD. The fatty acid ester of 3-chloropropane-1,2-diol can give 3-chloropropane-1,2-diol by liberation of fatty acid. It is said that if 3-chloropropane-1,2-diol and its derivatives are present in high concentrations, they will have a negative effect on health. However, trace amounts of 3-chloropropane-1,2-diol present in oils and fats such as vegetable oil that have been ingested over many years are not considered to have an immediate adverse effect on health, and 3-chloropropane-1,2- Although the intake standard value of diol is not defined, it is required to reduce its presence in the glyceride composition as much as possible.
上記課題に対して、例えば特許文献１には、３−クロロプロパン−１，２−ジオール、３−クロロプロパン−１，２−ジオールの脂肪酸エステル、グリシドール及びグリシドールの脂肪酸エステルからなる群より選ばれる少なくとも１種を含有し、及び／又は、ジグリセリドを３質量％以上含有するグリセリド組成物を、特定の温度条件にて脱臭処理等する方法が開示されている。この方法によれば、グリセリド組成物中のグリシドールの脂肪酸エステルや３−クロロプロパン−１，２−ジオールの脂肪酸エステル等の含有量を低減できる。また、特許文献２には、脱臭工程を経ていないグリセリド組成物とアルカリ白土とを接触させることにより、３−クロロプロパン−１，２−ジオール、及び３−クロロプロパン−１，２−ジオールの脂肪酸エステルの少ない精製グリセリド組成物、及び該精製グリセリド組成物の製造方法を提供することを開示する。しかし、グリセリド組成物は、精製後の加工等により３−クロロプロパン−１，２−ジオール等が増加することもあるため、更なる３−クロロプロパン−１，２−ジオール、及び３−クロロプロパン−１，２−ジオールの脂肪酸エステルの除去が求められている。また、上記特許文献１及び２は、３−クロロプロパン−１，２−ジオール、及び３−クロロプロパン−１，２−ジオールの脂肪酸エステルの生成を抑えるために２４０℃或いは２６０℃以下で脱臭しなければならず、風味をよくするために更に高温で脱臭することや、その後の工程で２６０℃以上のような高温に加熱することができなかった For example, Patent Document 1 discloses at least one selected from the group consisting of 3-chloropropane-1,2-diol, fatty acid ester of 3-chloropropane-1,2-diol, glycidol and fatty acid ester of glycidol. A method of deodorizing a glyceride composition containing seeds and / or containing 3% by mass or more of diglyceride under specific temperature conditions is disclosed. According to this method, the content of fatty acid ester of glycidol, fatty acid ester of 3-chloropropane-1,2-diol and the like in the glyceride composition can be reduced. Patent Document 2 discloses that 3-chloropropane-1,2-diol and fatty acid esters of 3-chloropropane-1,2-diol can be obtained by contacting a glyceride composition that has not undergone a deodorizing step with alkali clay. Disclosed are low purified glyceride compositions and methods for producing the purified glyceride compositions. However, since the glyceride composition may increase 3-chloropropane-1,2-diol and the like due to processing after purification, etc., further 3-chloropropane-1,2-diol and 3-chloropropane-1, There is a need to remove 2-diol fatty acid esters. In addition, in Patent Documents 1 and 2, deodorization must be performed at 240 ° C. or 260 ° C. or lower in order to suppress the formation of 3-chloropropane-1,2-diol and fatty acid esters of 3-chloropropane-1,2-diol. In addition, in order to improve the flavor, it was not possible to deodorize at a higher temperature, and it was not possible to heat to a high temperature such as 260 ° C. or higher in the subsequent steps.
このように、グリセリド組成物中の３−クロロプロパン−１，２−ジオール、及び３−クロロプロパン−１，２−ジオールの脂肪酸エステルの含有量をさらに効果的に低減する方法が検討されている。 Thus, a method for further effectively reducing the contents of 3-chloropropane-1,2-diol and fatty acid esters of 3-chloropropane-1,2-diol in the glyceride composition has been studied.
本発明は、かかる事情に鑑みてなされたものであり、３−クロロプロパン−１，２−ジオール、及び３−クロロプロパン−１，２−ジオールの脂肪酸エステルの少ない精製グリセリド組成物、及び該精製グリセリド組成物の製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and a purified glyceride composition with a small amount of 3-chloropropane-1,2-diol and a fatty acid ester of 3-chloropropane-1,2-diol, and the purified glyceride composition. It aims at providing the manufacturing method of a thing.
本発明者らは、上記課題を解決するために鋭意研究した結果、脱臭工程を経ていないグリセリド組成物と、白土及び炭酸カリウムを含む混合物とを接触させることで、精製グリセリド組成物中の３−クロロプロパン−１，２−ジオール、及び３−クロロプロパン−１，２−ジオールの脂肪酸エステルの生成が抑制され、これらの含有量が低減することを見出し、本発明を完成するに至った。具体的には、以下のようなものを提供する。 As a result of earnest research to solve the above-mentioned problems, the present inventors contacted a glyceride composition that has not undergone a deodorization step with a mixture containing clay and potassium carbonate, thereby bringing the 3-glyceride composition in the purified glyceride composition into contact. It was found that the production of chloropropane-1,2-diol and fatty acid esters of 3-chloropropane-1,2-diol was suppressed and the content thereof was reduced, and the present invention was completed. Specifically, the following are provided.
本発明の態様は、以下のとおりであってもよい。
〔１〕 脱臭工程を経ていないグリセリド組成物と、白土及び炭酸カリウムを含む混合物とを接触させる白土処理工程を含む、精製グリセリド組成物の製造方法。
〔２〕 前記白土がアルカリ白土である、前記〔１〕に記載の精製グリセリド組成物の製造方法。
〔３〕 前記炭酸カリウムの含有量が、前記脱臭工程を経ていないグリセリド組成物の全体の質量に対し、０．０１〜１０質量％である、前記〔１〕又は〔２〕に記載の精製グリセリド組成物の製造方法。
〔４〕 前記グリセリド組成物が、パーム由来の油脂である、前記〔１〕〜〔３〕のいずれか１項に記載の精製グリセリド組成物の製造方法。
〔５〕 前記白土処理工程の前に、さらに前記グリセリド組成物の脱ガム工程を含む、前記〔１〕〜〔４〕のいずれか１項に記載の精製グリセリド組成物の製造方法。
〔６〕 前記脱ガム工程が、前記グリセリド組成物と、リン酸又はクエン酸の水溶液、又はリン酸とを接触させ、前記白土処理工程でガム質を除去することを含む、前記〔５〕に記載の精製グリセリド組成物の製造方法。
〔７〕 前記白土処理工程が脱色工程であり、前記白土処理工程の後に、さらに脱臭工程を含む、前記〔１〕〜〔６〕のいずれか１項に記載の精製グリセリド組成物の製造方法。
〔８〕 前記脱臭工程が、１００〜２６０℃の温度条件下にて行われる、前記〔１〕〜〔７〕のいずれか１項に記載の精製グリセリド組成物の製造方法。
〔９〕 脱臭工程を経ていないグリセリド組成物と、白土及び炭酸カリウムを含む混合物とを接触させる白土処理工程を含む、グリセリド組成物の処理方法。
〔１０〕 前記グリセリド組成物が、パーム由来の油脂であり、前記白土がアルカリ白土であり、及び、前記炭酸カリウムの含有量が、前記脱臭工程を経ていないグリセリド組成物の全体の質量に対し、０．３〜１．０質量％である、前記〔９〕に記載のグリセリド組成物の処理方法。
〔１１〕 前記白土処理工程の前に、さらに前記グリセリド組成物の脱ガム工程を含み、前記脱ガム工程が、前記グリセリド組成物とリン酸又はクエン酸の水溶液、又はリン酸とを接触させ、前記白土処理工程でガム質を除去することを含む、前記〔９〕又は〔１０〕に記載のグリセリド組成物の処理方法。
〔１２〕 前記脱臭工程が、１００〜２６０℃の温度条件下にて行われる、前記〔９〕〜〔１１〕のいずれか１項に記載のグリセリド組成物の処理方法。
〔１３〕 ３−クロロプロパン−１，２−ジオール及び３−クロロプロパン−１，２−ジオールの脂肪酸エステルの含有量が、精製グリセリド組成物全体の質量に対し、１ｐｐｍ以下である、前記〔１〕〜〔８〕のいずれか１項に記載の製造方法により得られることを特徴とする精製グリセリド組成物。
Aspects of the present invention may be as follows.
[1] A method for producing a purified glyceride composition, comprising a clay treatment step in which a glyceride composition that has not undergone a deodorization step is contacted with a mixture containing clay and potassium carbonate.
[2] The method for producing a purified glyceride composition according to [1], wherein the clay is alkaline clay.
[3] The purified glyceride according to [1] or [2], wherein the content of the potassium carbonate is 0.01 to 10% by mass with respect to the total mass of the glyceride composition not subjected to the deodorization step. A method for producing the composition.
[4] The method for producing a purified glyceride composition according to any one of [1] to [3], wherein the glyceride composition is palm-derived oil.
[5] The method for producing a purified glyceride composition according to any one of [1] to [4], further including a degumming step of the glyceride composition before the clay treatment step.
[6] In the above [5], the degumming step includes bringing the glyceride composition into contact with an aqueous solution of phosphoric acid or citric acid, or phosphoric acid, and removing gum in the clay treatment step. The manufacturing method of the refinement | purification glyceride composition of description.
[7] The method for producing a purified glyceride composition according to any one of [1] to [6], wherein the white clay treatment step is a decolorization step, and further includes a deodorization step after the white clay treatment step.
[8] The method for producing a purified glyceride composition according to any one of [1] to [7], wherein the deodorizing step is performed under a temperature condition of 100 to 260 ° C.
[9] A method for treating a glyceride composition, comprising a clay treatment step in which a glyceride composition that has not undergone a deodorization step is contacted with a mixture containing clay and potassium carbonate.
[10] The glyceride composition is palm-derived oil and fat, the clay is alkaline clay, and the content of the potassium carbonate is based on the total mass of the glyceride composition not subjected to the deodorization step. The processing method of the glyceride composition as described in said [9] which is 0.3-1.0 mass%.
[11] Prior to the clay treatment step, further including a degumming step of the glyceride composition, the degumming step, the glyceride composition and an aqueous solution of phosphoric acid or citric acid, or phosphoric acid, The method for treating a glyceride composition according to [9] or [10], comprising removing gum in the clay treatment step.
[12] The method for treating a glyceride composition according to any one of [9] to [11], wherein the deodorizing step is performed under a temperature condition of 100 to 260 ° C.
[13] The content of fatty acid esters of 3-chloropropane-1,2-diol and 3-chloropropane-1,2-diol is 1 ppm or less with respect to the total mass of the purified glyceride composition, [8] A purified glyceride composition obtained by the production method according to any one of [8].
本発明によれば、３−クロロプロパン−１，２−ジオール、及び３−クロロプロパン−１，２−ジオールの脂肪酸エステルの少ない精製グリセリド組成物を得ることができる。
本発明により白土と炭酸カリウムの混合物で処理されたグリセリド組成物は、その後の脱臭工程で例えば１００℃以上の高温に晒されても、３−クロロプロパン−１，２−ジオール、及び３−クロロプロパン−１，２−ジオールの脂肪酸エステルの生成を抑えることができる。
According to the present invention, it is possible to obtain a purified glyceride composition with less 3-chloropropane-1,2-diol and 3-chloropropane-1,2-diol fatty acid ester.
Even if the glyceride composition treated with a mixture of clay and potassium carbonate according to the present invention is exposed to a high temperature of, for example, 100 ° C. or higher in the subsequent deodorization step, 3-chloropropane-1,2-diol and 3-chloropropane- Generation of 1,2-diol fatty acid ester can be suppressed.
以下、本発明の実施形態について具体的に説明する。
［精製グリセリド組成物の製造方法］
本発明の精製グリセリド組成物の製造方法は、脱臭工程を経ていないグリセリド組成物の任意の脱ガム工程、前記任意に脱ガムしたグリセリド組成物と白土及び炭酸カリウムを含む混合物とを接触させる白土処理工程、前記接触後のグリセリド組成物の任意の脱臭工程を含む。以下、各工程について説明する。
Hereinafter, embodiments of the present invention will be specifically described.
[Method for producing purified glyceride composition]
The method for producing a purified glyceride composition of the present invention includes an arbitrary degumming step of a glyceride composition that has not undergone a deodorizing step, and a white clay treatment in which the arbitrarily degummed glyceride composition is contacted with a mixture containing white clay and potassium carbonate. Step, optional deodorizing step of the glyceride composition after the contact. Hereinafter, each step will be described.
［白土処理工程］
本発明の精製グリセリド組成物の製造方法は、脱臭工程を経ていないグリセリド組成物と、白土及び炭酸カリウムを含む混合物とを接触させる白土処理工程を含む。なお、本発明の白土処理工程は、脱色工程であってもよい。
（脱臭工程を経ていないグリセリド組成物）
本発明の脱臭工程を経ていないグリセリド組成物は、精製完了前の組成のグリセリド組成物を意味する。ここで、本発明で言うグリセリド組成物は、グリセリンに脂肪酸が１〜３個エステル結合したグリセリドを含むものであり、油脂の主要成分であるトリグリセリド（トリアシルグリセロール）の他、ジグリセリド（ジアシルグリセロール）、モノグリセリド（モノアシルグリセロール）も含むものとする。また、動植物油脂由来のグリセリド以外の成分、例えば、植物ステロール、レシチン、抗酸化成分、色素成分等が含まれてもよいが、９５質量％以上はグリセリドであることが好ましく、より好ましくは、９７質量％以上、更に好ましくは９９質量％以上、特に好ましくは１００質量％がグリセリドであることが適当である。なお、グリセリド中のトリグリセリドは、９０質量％以上が好ましく、より好ましくは９３質量％〜１００質量％であることが適当である。
具体的なグリセリド組成物としては、未精製の粗油、定法に従って精製された脱ガム油、脱酸油、もしくは脱色油が好ましく、脱酸油もしくは脱色油がより好ましい。例えば、菜種油、大豆油、米油、サフラワー油、ぶどう油、ひまわり油、小麦はい芽油、とうもろこし油、綿実油、ごま油、落花生油、フラックス油、エゴマ油、オリーブ油、パーム油、ヤシ油等の植物油、これら２種以上を混合した調合植物油、又は、これらを分別したパームオレイン、パームステアリン、パームスーパーオレイン、パームミッドフラクション等の食用分別油、これらの粗油、水素添加油、エステル交換油等のほか、中鎖脂肪酸トリグリセリドのような直接エステル化反応により製造された食用油を用いることができる。なお、３−ＭＣＰＤ、及び／又は３−ＭＣＰＤの脂肪酸エステルは、部分グリセリドが比較的多い油脂において多く発生する傾向にあることから、パーム由来の油脂、米油、エステル交換油等を原料に用いることが本発明の３−ＭＣＰＤ、及び／又は３−ＭＣＰＤの脂肪酸エステルの低減効果が高いという理由から特に好ましい。パーム由来の油脂としては、パーム油、パーム核油、パームオレイン、パームステアリン、パームスーパーオレイン、パームミッドフラクション等が挙げられる。本発明の白土処理工程の前後の精製方法は、定法を用いることができる。具体的には、ケミカル精製（ケミカルリファイニング）と、フィジカル精製（フィジカルリファイニング）とがあるが、いずれの精製方法を用いてもよい。なお、前者のケミカル精製は、原料となる植物を圧搾・抽出した原油が、脱ガム処理、脱酸処理、脱色処理、脱ろう処理、脱臭処理を経ることで精製され、精製油となる。これに対し、後者のフィジカル精製は、パーム油やヤシ油等にてよく行われている方法であり、原料となるパームやヤシ等を圧搾した原油が、脱ガム処理、脱色処理、脱酸・脱臭処理を経ることで精製され、精製油となる。
「脱臭工程を経ていない」とは、後述する脱臭工程で処理する前、を意味するものであるが、具体的には、例えば１００℃以上、好ましくは１５０℃以上、より好ましくは１８０℃以上、更に好ましくは２００℃以上、特に好ましくは２４０℃以上の温度で加熱されていないことを意味する。当該脱臭工程、特に、このような温度で加熱される脱臭工程を経ることにより、３−クロロプロパン−１，２−ジオール及び３−クロロプロパン−１，２−ジオールの脂肪酸エステルが増加するため、本発明は、これらの温度に加熱する前に後述する白土処理を行い、３−クロロプロパン−１，２−ジオール及び３−クロロプロパン−１，２−ジオールの脂肪酸エステルが生成する原因物質（塩素化合物等）を除去するものである。脱臭工程を経ていなければ、脱ガム工程、脱酸工程、水洗工程等の他の精製工程を経た精製油を用いてもよい。脱臭工程を経ていないグリセリド組成物は、３−ＭＣＰＤ、及び／３−ＭＣＰＤの脂肪酸エステルが生成していない点で好ましい。
[White clay treatment process]
The method for producing a purified glyceride composition of the present invention includes a clay treatment step in which a glyceride composition that has not undergone a deodorization step and a mixture containing clay and potassium carbonate are contacted. The white clay treatment process of the present invention may be a decolorization process.
(Glyceride composition not subjected to deodorization process)
The glyceride composition that has not undergone the deodorizing step of the present invention means a glyceride composition having a composition before completion of purification. Here, the glyceride composition referred to in the present invention includes glycerin in which 1 to 3 fatty acids are ester-bonded to glycerin. In addition to triglyceride (triacylglycerol) which is a main component of fats and oils, diglyceride (diacylglycerol) And monoglycerides (monoacylglycerols). Further, components other than glycerides derived from animal and vegetable oils and fats, for example, plant sterols, lecithins, antioxidant components, pigment components, etc. may be contained, but 95% by mass or more is preferably glycerides, more preferably 97 It is appropriate that glyceride is not less than mass%, more preferably not less than 99 mass%, particularly preferably 100 mass%. In addition, 90 mass% or more is preferable, and, as for the triglyceride in glyceride, it is suitable that it is 93 mass%-100 mass% more preferably.
As a specific glyceride composition, unrefined crude oil, degummed oil purified according to a conventional method, deoxidized oil, or decolorized oil are preferable, and deoxidized oil or decolorized oil is more preferable. For example, rapeseed oil, soybean oil, rice oil, safflower oil, grape oil, sunflower oil, wheat germ oil, corn oil, cottonseed oil, sesame oil, peanut oil, flux oil, sesame oil, olive oil, palm oil, coconut oil, etc. Vegetable oil, mixed vegetable oil obtained by mixing two or more of these, or edible fractionated oil such as palm olein, palm stearin, palm super olein, palm mid fraction, etc., these crude oil, hydrogenated oil, transesterified oil, etc. Besides, edible oil produced by direct esterification reaction such as medium chain fatty acid triglyceride can be used. Since 3-MCPD and / or 3-MCPD fatty acid esters tend to occur in fats and oils with a relatively large amount of partial glycerides, palm-derived oils, rice oils, transesterified oils, etc. are used as raw materials. It is particularly preferable because the effect of reducing 3-MCPD and / or 3-MCPD fatty acid ester of the present invention is high. Examples of palm-derived oils and fats include palm oil, palm kernel oil, palm olein, palm stearin, palm super olein, and palm mid-fraction. A conventional method can be used for the purification method before and after the clay treatment process of the present invention. Specifically, there are chemical refining (chemical refining) and physical refining (physical refining), and any refining method may be used. In the former chemical refining, crude oil obtained by squeezing and extracting a plant as a raw material is refined through degumming, deoxidation, decolorization, dewaxing, and deodorization to become refined oil. On the other hand, the latter physical refining is a method that is often performed with palm oil, palm oil, etc., and crude oil obtained by squeezing palm or palm as a raw material is subjected to degumming treatment, decolorization treatment, deoxidation / It is refined through deodorizing treatment and becomes refined oil.
“Undeodorized step” means before treatment in the deodorizing step described later, specifically, for example, 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 180 ° C. or higher, More preferably, it means that it is not heated at a temperature of 200 ° C. or higher, particularly preferably 240 ° C. or higher. Since the deodorizing step, particularly the deodorizing step heated at such a temperature, increases the fatty acid esters of 3-chloropropane-1,2-diol and 3-chloropropane-1,2-diol, the present invention. Performs the clay treatment described later before heating to these temperatures, and causes causative substances (chlorine compounds, etc.) to produce 3-chloropropane-1,2-diol and fatty acid esters of 3-chloropropane-1,2-diol. To be removed. If the deodorization process has not been performed, refined oil that has undergone another purification process such as a degumming process, a deoxidation process, or a water washing process may be used. A glyceride composition that has not undergone a deodorization step is preferred in that 3-MCPD and / 3-MCPD fatty acid esters are not produced.
（白土）
本発明で用いられる白土としては、活性白土、中性白土、酸性白土、アルカリ白土が挙げられる。白土としては、活性白土及びアルカリ白土がより好ましく、アルカリ白土が特に好ましい。
活性白土としては、例えば、白土や酸性白土を酸で活性化したものを挙げることができる。活性白土および酸性白土のｐＨは、例えば１．０以上、好ましくはｐＨが２．０以上、より好ましくはｐＨが３．０以上であって、例えばｐＨが６．０以下、好ましくはｐＨが５．０以下、より好ましくはｐＨが４．０以下を呈する白土が、３−ＭＣＰＤの原因物質となり得る塩素化合物に対する吸着能及び分解能が高いため好ましい。上記ｐＨの上限及び下限は適宜組み合わせた範囲としてもよく、また、例えば、ｐＨ＝１．０〜６．０の範囲が好ましく、より好ましくはｐＨ＝２．０〜５．０、特に好ましくはｐＨ＝３．０〜４．０であることが適当である。
特に、アルカリ白土としては、水中に白土を添加した場合に、当該アルカリ白土を含む水溶液のｐＨがアルカリ性を呈する白土（すなわち、アルカリ性の白土）であれば特に限定されるものではないが、例えばｐＨが７．５以上、好ましくはｐＨが８．０以上、より好ましくはｐＨが８．５以上であって、例えばｐＨが１２以下、好ましくはｐＨが１１以下、より好ましくはｐＨが１０以下を呈する白土が、３−ＭＣＰＤの原因物質となり得る塩素化合物に対する吸着能及び分解能が高いため好ましい。上記ｐＨの上限及び下限は適宜組み合わせた範囲としてもよく、また、例えば、ｐＨ＝７．５〜１２の範囲が好ましく、より好ましくはｐＨ＝８．０〜１０、特に好ましくはｐＨ＝８．５〜９であることが適当である。
(White clay)
Examples of the clay used in the present invention include activated clay, neutral clay, acidic clay, and alkaline clay. As the clay, activated clay and alkali clay are more preferable, and alkali clay is particularly preferable.
Examples of the activated clay include those obtained by activating a clay or an acid clay with an acid. The pH of the activated clay and the acid clay is, for example, 1.0 or more, preferably 2.0 or more, more preferably 3.0 or more, for example, pH 6.0 or less, preferably pH 5 A clay with a pH of not more than 0.0, more preferably not more than 4.0 is preferable because of its high adsorptivity and resolution for chlorine compounds that can cause 3-MCPD. The upper limit and the lower limit of the pH may be appropriately combined, and for example, a range of pH = 1.0 to 6.0 is preferable, more preferably pH = 2.0 to 5.0, and particularly preferably pH. = 3.0-4.0 is appropriate.
In particular, the alkaline clay is not particularly limited as long as the pH of the aqueous solution containing the alkaline clay is alkaline when the clay is added to water (that is, alkaline clay). Is 7.5 or more, preferably pH 8.0 or more, more preferably pH 8.5 or more, for example, pH 12 or less, preferably pH 11 or less, more preferably pH 10 or less. White clay is preferred because of its high adsorptive capacity and resolution for chlorine compounds that can cause 3-MCPD. The upper limit and lower limit of the pH may be appropriately combined, and for example, a range of pH = 7.5 to 12 is preferable, more preferably pH = 8.0 to 10, and particularly preferably pH = 8.5. It is suitable that it is ~ 9.
本発明で使用されるアルカリ白土としては、特に限定されないが、例えば、下記の組成（単位：アルカリ白土全量に対する質量％）を有するものを使用できる。
ＳｉＯ2 （５０〜６０質量％）
Ａｌ2Ｏ3 （１０〜２０質量％）
Ｆｅ2Ｏ3 （３〜１０質量％）
ＭｇＯ （２〜９質量％）
ＣａＯ （１〜５質量％）
Although it does not specifically limit as alkali clay used by this invention, For example, what has the following composition (unit: the mass% with respect to the total amount of alkali clay) can be used.
SiO 2 (50-60% by mass)
Al 2 O 3 (10 to 20% by mass)
Fe 2 O 3 (3 to 10% by mass)
MgO (2-9 mass%)
CaO (1-5% by mass)
白土処理工程において使用される白土の量は、グリセリド組成物中の塩素化合物を有効に吸着もしくは分解し、精製グリセリド組成物中の３−ＭＣＰＤ及び／又は３−ＭＣＰＤの脂肪酸エステルの生成を抑制し、これらの含有量についての十分な低減効果を得るために、原料となる脱臭工程を経ていないグリセリド組成物の量に対して、例えば０．５質量％以上、好ましくは０．６質量％以上、より好ましくは０．７質量％以上、更に好ましくは０．８質量％以上、特に好ましくは１質量％以上、ことさら好ましくは１．５質量％以上であり、例えば１０質量％以下、好ましくは９質量％以下、より好ましくは７質量％以上、更に好ましくは５質量％以下、特に好ましくは３質量％以下、ことさら好ましくは２％質量以下であることが好ましい。上記白土の量の上限及び下限は適宜組み合わせた範囲としてもよく、また、例えば、０．５〜１０質量％の範囲が好ましく、より好ましくは０．７〜７質量％、特に好ましくは１〜３質量％であることが適当である。 The amount of clay used in the clay treatment process effectively adsorbs or decomposes chlorine compounds in the glyceride composition, and suppresses the production of 3-MCPD and / or 3-MCPD fatty acid ester in the purified glyceride composition. In order to obtain a sufficient reduction effect for these contents, for example, 0.5% by mass or more, preferably 0.6% by mass or more, with respect to the amount of the glyceride composition that has not undergone the deodorizing step as a raw material, More preferably 0.7% by mass or more, further preferably 0.8% by mass or more, particularly preferably 1% by mass or more, still more preferably 1.5% by mass or more, for example, 10% by mass or less, preferably 9% by mass. % Or less, more preferably 7% by mass or more, further preferably 5% by mass or less, particularly preferably 3% by mass or less, and even more preferably 2% by mass or less. . The upper limit and the lower limit of the amount of the white clay may be appropriately combined. For example, the range of 0.5 to 10% by mass is preferable, more preferably 0.7 to 7% by mass, and particularly preferably 1 to 3%. It is suitable that it is mass%.
（炭酸カリウム）
本発明では、炭酸カリウムを白土と共に使用して白土処理工程が行われる。炭酸カリウムの含有量としては、前記脱臭工程を経ていないグリセリド組成物の全体の質量に対し、例えば０．０１質量％以上、好ましくは０．０５質量％以上、より好ましくは０．１質量％以上、更に好ましくは０．２質量％以上、特に好ましくは０．３質量％以上であり、また、１０質量％以下、好ましくは５質量％以下、より好ましくは２質量％以下、更に好ましくは１質量％以下、特に好ましくは０．５質量％以下である。これら炭酸カリウムの量の上限及び下限は適宜組み合わせた範囲としてもよく、例えば、０．０１〜１０質量％、好ましくは０．０５〜５質量％、より好ましくは０．１〜１質量％、更に好ましくは０．１〜０．５質量％、特に好ましくは０．３〜０．５質量％であることが適当である。
(Potassium carbonate)
In the present invention, the white clay treatment step is performed using potassium carbonate together with white clay. As content of potassium carbonate, it is 0.01 mass% or more with respect to the whole mass of the glyceride composition which has not passed through the said deodorizing process, Preferably it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more. More preferably, it is 0.2% by mass or more, particularly preferably 0.3% by mass or more, and 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass. % Or less, particularly preferably 0.5% by mass or less. The upper limit and lower limit of the amount of potassium carbonate may be appropriately combined, for example, 0.01 to 10% by mass, preferably 0.05 to 5% by mass, more preferably 0.1 to 1% by mass, and further It is preferably 0.1 to 0.5% by mass, particularly preferably 0.3 to 0.5% by mass.
（白土及び炭酸カリウムを含む混合物）
本発明で使用する白土及び炭酸カリウムを含む混合物は、上述の白土及び炭酸カリウムを含み、かつそれぞれの活性を損なわない限り、いかなる混合物であってもよい。本発明の混合物には、白土及び炭酸カリウムの他、活性炭、シリカ等を含み得る。
混合物中の白土と炭酸カリウムとの質量比は、例えば、白土：炭酸カリウム＝５０：１〜１：１０、好ましくは４０：１〜１：５であり、より好ましくは３０：１〜１：１であり、更に好ましくは２５：１〜２：１であり、特に好ましくは２０：１〜４：１であることが適当である。
(Mixture containing white clay and potassium carbonate)
The mixture containing clay and potassium carbonate used in the present invention may be any mixture as long as it contains the above clay and potassium carbonate and does not impair the activity of each. The mixture of the present invention may contain activated carbon, silica and the like in addition to clay and potassium carbonate.
The mass ratio of white clay and potassium carbonate in the mixture is, for example, white clay: potassium carbonate = 50: 1 to 1:10, preferably 40: 1 to 1: 5, and more preferably 30: 1 to 1: 1. More preferably, it is 25: 1 to 2: 1, and particularly preferably 20: 1 to 4: 1.
（白土処理工程の条件）
白土処理工程における各種条件は特に制限されず、通常の油脂の製造方法で使用される脱色工程の条件を用いることができる。例えば、原料である脱臭工程を経ていないグリセリド組成物に白土及び炭酸カリウムを含む混合物を加えた後、例えば、７０〜２００℃、好ましくは８０〜１５０℃、より好ましくは９０〜１２０℃の温度で、例えば、５〜１２０分間、好ましくは１０〜９０分間、より好ましくは１５〜６０分間加熱してもよい。白土処理工程を終えた後は、ろ過又は遠心分離等により白土及び炭酸カリウムを含む混合物を除去し、白土処理されたグリセリド組成物（脱色油）を得ることができる。白土に含まれる水分を除去して、吸着能力を高めるために減圧下で脱色することが好ましい。圧力（減圧度）は、例えば、２００００Ｐａ以下、好ましくは、３００〜１３０００Ｐａ、より好ましくは２０００〜１００００Ｐａの減圧下が好ましい。
(Conditions for white clay treatment process)
Various conditions in the white clay treatment process are not particularly limited, and the conditions of the decolorization process used in the normal method for producing fats and oils can be used. For example, after adding a mixture containing clay and potassium carbonate to a glyceride composition that has not undergone a deodorizing step as a raw material, for example, at a temperature of 70 to 200 ° C, preferably 80 to 150 ° C, more preferably 90 to 120 ° C. For example, you may heat for 5 to 120 minutes, Preferably it is 10 to 90 minutes, More preferably, you may heat for 15 to 60 minutes. After finishing the clay treatment process, the mixture containing clay and potassium carbonate is removed by filtration or centrifugation, and a clay-treated glyceride composition (decolorized oil) can be obtained. It is preferable to decolorize under reduced pressure in order to remove moisture contained in the white clay and increase the adsorption capacity. The pressure (degree of reduced pressure) is, for example, 20000 Pa or less, preferably 300 to 13000 Pa, more preferably 2000 to 10,000 Pa under reduced pressure.
原料のグリセリド組成物と、白土及び炭酸カリウムを含む混合物とを接触させる方法は特に限定されず、例えば、白土や活性炭で脱色工程を行った後に、白土を用いて処理を行うこともできる。例えば、上記接触される原料を脱色処理槽等に投入し、原料を任意に撹拌することによって行われてもよい。脱色処理槽としては、例えば、タンク、カラム、ろ過器などを用いることができる。タンクの場合は、攪拌機付のタンクであることが好ましく、原料のグリセリド組成物と白土及び炭酸カリウムを含む混合物を接触した後、ろ過もしくは遠心分離機等で上記混合物を分離することが好ましい。ろ過を容易にするために、白土処理工程を、ろ過助剤等の助剤の存在下で行われていてもよい。ろ過助剤としては、例えば、セライトなどの無機ろ過助剤及びセルロースなどの繊維やその粉砕物などの有機ろ過助剤が挙げられる。また、カラムやろ過器に白土を充填・保持し、原料のグリセリド組成物を当該カラムやろ過器に通液してもよい。原料のグリセリド組成物を通液することにより、通液と同時に上記混合物も分離でき、装置もタンクに比べてコンパクトになるので好ましい。ろ過器としては、例えば、単板ろ過器、フィルタープレス、アマフィルター等を用いることが好ましい。タンク、カラム、ろ過器は、ガラス製、プラスチック製もしくは鉄、ステンレスなどの金属製を用いることができるが、耐久性の点から金属製であることが好ましい。本白土処理工程は、原料のグリセリド組成物の脱色も行うことができる。 The method for bringing the raw material glyceride composition into contact with the mixture containing clay and potassium carbonate is not particularly limited. For example, after performing the decoloring step with clay or activated carbon, the clay can be treated with clay. For example, the raw material to be contacted may be put into a decolorization treatment tank or the like, and the raw material may be arbitrarily stirred. As the decolorization treatment tank, for example, a tank, a column, a filter, or the like can be used. In the case of a tank, it is preferable that the tank is equipped with a stirrer, and it is preferable to separate the mixture by filtration or a centrifuge after contacting the raw material glyceride composition with a mixture containing clay and potassium carbonate. In order to facilitate filtration, the clay treatment process may be performed in the presence of an auxiliary agent such as a filter auxiliary. Examples of the filter aid include inorganic filter aids such as celite and organic filter aids such as fibers such as cellulose and pulverized products thereof. Alternatively, white clay may be filled and held in a column or filter, and the raw glyceride composition may be passed through the column or filter. By passing the starting glyceride composition, the mixture can be separated simultaneously with the passing, and the apparatus is also more compact than the tank, which is preferable. As the filter, for example, a single plate filter, a filter press, an flax filter, or the like is preferably used. The tank, column, and filter can be made of glass, plastic, or metal such as iron or stainless steel, but are preferably made of metal from the viewpoint of durability. In this white clay treatment step, the raw material glyceride composition can also be decolorized.
［脱ガム工程］
上記白土処理工程に先立って、脱臭工程を経ていないグリセリド組成物を脱ガムする任意の脱ガム工程を含んでもよい。
脱ガム工程としては、油脂の脱ガムで通常使用されている工程を採用することができるが、例えば、上記グリセリド組成物と酸とを水中で接触させ、その後得られた水相を分離除去することによって行われてもよい。酸としては、例えば、リン酸、クエン酸、シュウ酸、コハク酸等が挙げられ、好ましくはリン酸又はクエン酸である。酸は、１種の酸又は２種以上の酸を組み合わせて使用してもよい。酸の含有量は、接触されるグリセリド組成物の質量を１００質量％とした場合、例えば、０．００１質量％以上、好ましくは、０．００５質量％以上、より好ましくは０．０１質量％以上、更に好ましくは０．０２質量％以上であり、また、例えば、１質量％以下、好ましくは、０．５質量％以下、より好ましくは０．１質量％以下、更に好ましくは０．０７質量％以下であることが適当である。これら上限値及び下限値は適宜組み合わせて任意の範囲としてもよい。酸の含有量として特に好ましくは０．０４質量％又は０．０５質量％である。
上記酸は、水溶液として添加することが、充分に油脂と接触させるためには好ましい。上記酸に水を添加する場合、接触されるグリセリド組成物の質量を１００質量％とした場合、水の添加量は、例えば、０．００２〜１質量％であることが適当である。
[Degumming process]
Prior to the clay treatment step, an optional degumming step of degumming the glyceride composition that has not undergone the deodorization step may be included.
As the degumming step, a step usually used in fat degumming can be employed. For example, the glyceride composition and an acid are contacted in water, and then the obtained aqueous phase is separated and removed. May be performed. Examples of the acid include phosphoric acid, citric acid, oxalic acid, succinic acid and the like, preferably phosphoric acid or citric acid. The acid may be used in combination of one acid or two or more acids. The content of the acid is, for example, 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, when the mass of the glyceride composition to be contacted is 100% by mass. Further, it is preferably 0.02% by mass or more, and for example, 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and further preferably 0.07% by mass. The following is appropriate. These upper limit value and lower limit value may be arbitrarily combined to form an arbitrary range. The acid content is particularly preferably 0.04% by mass or 0.05% by mass.
It is preferable to add the acid as an aqueous solution in order to sufficiently contact the oil. When adding water to the acid, when the mass of the glyceride composition to be contacted is 100% by mass, the amount of water added is suitably 0.002 to 1% by mass, for example.
脱ガム工程で析出するガム質は、次の工程である前述の白土処理工程で、白土とともに除去するか、脱ガム工程で分離除去することができる。脱ガム工程で分離除去する場合は、上記水相の分離除去により、水相に溶解するガム成分及び不純物を除去し、油相に存在するグリセリド組成物を得ることができる。分離方法としては、例えば、ろ過又は遠心分離法を挙げることができる。ろ過及び遠心分離の諸条件は、上述の白土処理工程におけるろ過及び遠心分離の条件を使用してもよい。ここで、ガム質とは、パーム粗油に含まれているリン脂質等である。 The gum which precipitates in the degumming step can be removed together with the white clay in the white clay treatment step, which is the next step, or can be separated and removed in the degumming step. When separating and removing in the degumming step, the above-mentioned aqueous phase is separated and removed to remove the gum component and impurities dissolved in the aqueous phase, thereby obtaining a glyceride composition present in the oil phase. Examples of the separation method include filtration or centrifugation. As the various conditions for filtration and centrifugation, the conditions for filtration and centrifugation in the above-described clay processing step may be used. Here, the gum is phospholipid and the like contained in palm crude oil.
［脱臭工程］
上記白土処理工程の後、白土及び炭酸カリウムを含む混合物と接触させて得た接触後のグリセリド組成物をさらに脱臭する、任意の脱臭工程を含んでもよい。
脱臭工程を含む場合、上記白土処理工程は、グリセリド組成物の脱色工程に相当し得る。脱臭は、上記接触後のグリセリド組成物を加熱し、任意に水蒸気を適用することによって行われる。加熱条件は、通常の油脂の製造方法で用いられる１００〜２６０℃の温度条件下で行ってもよく、従来の３−ＭＣＰＤ及び／又は３−ＭＣＰＤの脂肪酸エステルが増大する条件の２４５〜２７０℃、あるいは２５０〜２７０℃で行ってもよい。また、より低い１００〜２５０℃の温度条件にて行ってもよい。脱臭工程において好ましい温度条件は１５０〜２５０℃であり、より好ましくは１８０〜２５０℃であり、さらに好ましくは１８０〜２３０℃である。好ましくは、通常の油脂の製造方法で用いられる温度条件よりも低い温度条件下でグリセリド組成物の脱臭を行うことにより、精製グリセリド組成物中の３−ＭＣＰＤ及び／又は３−ＭＣＰＤの脂肪酸エステルの生成抑制効果、及びこれらの含有量の低減効果が大きくなることが期待できる。
[Deodorization process]
You may include the arbitrary deodorizing process which further deodorizes the glyceride composition after the contact obtained by making it contact with the mixture containing clay and potassium carbonate after the said clay treatment process.
When the deodorizing step is included, the clay treatment step can correspond to a decolorizing step of the glyceride composition. Deodorization is performed by heating the glyceride composition after the contact and optionally applying water vapor. The heating conditions may be performed under the temperature condition of 100 to 260 ° C. used in the usual method for producing fats and oils, and the conventional 3-MCPD and / or 3-MCPD fatty acid ester is increased at 245 to 270 ° C. Or you may carry out at 250-270 degreeC. Moreover, you may perform by lower temperature conditions of 100-250 degreeC. In the deodorization step, a preferable temperature condition is 150 to 250 ° C, more preferably 180 to 250 ° C, and further preferably 180 to 230 ° C. Preferably, 3-MCPD and / or 3-MCPD fatty acid ester in the purified glyceride composition is deodorized by deodorizing the glyceride composition under a temperature condition lower than the temperature condition used in a normal method for producing fats and oils. It can be expected that the effect of suppressing the production and the effect of reducing the content thereof will increase.
脱臭時間は、１５〜１５０分であることが好ましく、２０〜１００分であることがより好ましい。
前記加熱は、任意に減圧下で行ってもよい。減圧の条件は、例えば、１０〜１３００Ｐａ、好ましくは、４００〜１３００Ｐａ、より好ましくは６７０〜１３００Ｐａであることが適当である。
前記加熱は、水蒸気を精製グリセリド中に吹き込みながら行うことが好ましい。吹込む水蒸気量は、０．５〜１０質量％であることが好ましく、１〜５質量％であることがより好ましい。
The deodorization time is preferably 15 to 150 minutes, and more preferably 20 to 100 minutes.
The heating may optionally be performed under reduced pressure. The conditions for reducing the pressure are, for example, 10 to 1300 Pa, preferably 400 to 1300 Pa, and more preferably 670 to 1300 Pa.
The heating is preferably performed while blowing water vapor into the purified glyceride. The amount of steam to be blown is preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass.
（再精製工程）
本発明の精製グリセリド組成物の製造方法においては、上記白土処理工程又は任意の脱臭工程を経た精製グリセリド組成物を再度精製してもよい。再精製工程は、前述の精製工程を行うことができ、例えば、再ガム工程、再脱色工程、又は再脱臭工程を含むことができる。特に、再脱色工程を行うことが好ましい。再脱色工程において使用される白土としては特に制限されず、上記白土処理工程で使用した各種白土を使用することができる。
(Repurification process)
In the method for producing a purified glyceride composition of the present invention, the purified glyceride composition that has undergone the clay treatment step or any deodorizing step may be purified again. The re-purification step can perform the above-described purification step, and can include, for example, a re-gumming step, a re-decoloring step, or a re-deodorizing step. In particular, it is preferable to perform a recoloring step. The white clay used in the re-bleaching step is not particularly limited, and various white clays used in the white clay treatment step can be used.
再脱色工程の前の最初の脱色工程（上記白土処理工程）において、グリセリド組成物と白土及び炭酸カリウムを含む混合物とを接触させていれば、精製グリセリド組成物中の３−ＭＣＰＤの原因物質と考えられる塩素化合物の残留量が十分に低減される。そのため、再脱色工程において使用する白土の種類に関わらず、再脱色工程後の再脱臭工程において生成する可能性のある３−ＭＣＰＤの量を顕著に低減できる。 If the glyceride composition and the mixture containing clay and potassium carbonate are brought into contact with each other in the first decolorization process (the above-mentioned clay treatment process) before the recolorization process, the causative substance of 3-MCPD in the purified glyceride composition The possible residual amount of chlorine compounds is sufficiently reduced. Therefore, the amount of 3-MCPD that may be generated in the re-deodorizing step after the re-decoloring step can be significantly reduced regardless of the type of white clay used in the re-decoloring step.
再脱色工程における条件は特に制限されず、再脱色工程の前の最初の白土処理工程同様、通常の油脂の製造方法で使用される条件であってもよい。例えば、精製グリセリド組成物に白土を加えた後に、減圧下、８０〜１５０℃で５〜６０分間加熱してもよい。再脱色を終えた後は、ろ過等により白土を除去し、再脱色したグリセリド組成物を得ることができる。 The conditions in the re-bleaching step are not particularly limited, and may be the conditions used in the usual method for producing fats and oils, like the first clay processing step before the re-decoloring step. For example, after adding clay to the purified glyceride composition, it may be heated at 80 to 150 ° C. for 5 to 60 minutes under reduced pressure. After the re-bleaching is finished, the white clay is removed by filtration or the like, and a re-bleached glyceride composition can be obtained.
再脱色工程後に得られた再脱色グリセリド組成物を、さらに再脱臭してもよい。再脱臭工程における条件は特に制限されず、最初の脱臭工程同様、通常の油脂の製造方法で使用される条件であってもよい。 The re-bleaching glyceride composition obtained after the re-bleaching step may be further deodorized. The conditions in the re-deodorization step are not particularly limited, and may be the conditions used in the normal method for producing fats and oils, as in the first deodorization step.
［精製グリセリド組成物］
本発明の精製グリセリド組成物は、３−クロロプロパン−１，２−ジオール及び３−クロロプロパン−１，２−ジオール（３−ＭＣＰＤ）の脂肪酸エステルの含有量が、精製グリセリド組成物全体の質量に対し、１ｐｐｍ以下であることを特徴とする。
３−ＭＣＰＤの脂肪酸エステルの含有量は、好ましくは０．９ｐｐｍ以下、より好ましくは０．８ｐｐｍ以下、更に好ましくは０．７ｐｐｍ以下、特に好ましくは０．６ｐｐｍ以下、ことさら好ましくは０．５ｐｐｍ以下であることが適当である。３−ＭＣＰＤの脂肪酸エステルの含有量は低ければ低いほどよいので、その下限値を特に設ける必要はないが、例えば、好ましくは０．２ｐｐｍ以上、より好ましくは０．１ｐｐｍ以上、更に好ましくは０．０５ｐｐｍ以上、特に好ましくは０．０１ｐｐｍ以上、ことさら好ましくは０．００５ｐｐｍ以上である。本発明の精製グリセリド組成物は、上述の本発明の精製グリセリド組成物の製造方法により得られる。本発明の精製グリセリド組成物は、精製グリセリド組成物中の３−ＭＣＰＤ、及び３−ＭＣＰＤの脂肪酸エステルの含有量が好適に低減された組成物である。
[Purified glyceride composition]
In the purified glyceride composition of the present invention, the content of fatty acid esters of 3-chloropropane-1,2-diol and 3-chloropropane-1,2-diol (3-MCPD) is based on the total mass of the purified glyceride composition. 1 ppm or less.
The content of fatty acid ester of 3-MCPD is preferably 0.9 ppm or less, more preferably 0.8 ppm or less, still more preferably 0.7 ppm or less, particularly preferably 0.6 ppm or less, and even more preferably 0.5 ppm or less. It is appropriate to be. The lower the content of the fatty acid ester of 3-MCPD, the better. Therefore, it is not necessary to provide the lower limit value, but for example, it is preferably 0.2 ppm or more, more preferably 0.1 ppm or more, and still more preferably 0.8. It is at least 05 ppm, particularly preferably at least 0.01 ppm, even more preferably at least 0.005 ppm. The purified glyceride composition of the present invention is obtained by the above-described method for producing the purified glyceride composition of the present invention. The purified glyceride composition of the present invention is a composition in which the content of 3-MCPD and the fatty acid ester of 3-MCPD in the purified glyceride composition is suitably reduced.
［精製グリセリド組成物中の３−ＭＣＰＤ及び／又は３−ＭＣＰＤの含有量の特定］
本発明においては、上記白土処理工程により、精製グリセリド組成物中の３−ＭＣＰＤ及び／又は３−ＭＣＰＤの脂肪酸エステルの生成を抑制し、これらの含有量を低減させることができる。精製グリセリド組成物中の３−ＭＣＰＤ及び／又は３−ＭＣＰＤの脂肪酸エステルの含有量は、アメリカ油化学会公定法（ＡＯＣＳ Ｏｆｆｉｃｉａｌ Ｍｅｔｈｏｄ Ｃｄ２９ｃ−１３）に準拠して行うことができる。具体的には、精製グリセリド組成物中に含まれる３−ＭＣＰＤ及び３−ＭＣＰＤの脂肪酸エステルの量を、３−ＭＣＰＤの量として換算した総量（以下、「Ｔｒｕｅ ＭＣＰＤ」という）を求め、これを３−ＭＣＰＤの含有量とした。なお、精製グリセリド組成物中には、３−ＭＣＰＤ及び３−ＭＣＰＤの脂肪酸エステルに類似する化合物として、グリシドール及びグリシドールの脂肪酸エステルが含まれるが、上記方法により測定される３−ＭＣＰＤの含有量の中にこれらグリシドール及びその脂肪酸エステルは含まれない。
[Specification of content of 3-MCPD and / or 3-MCPD in purified glyceride composition]
In this invention, the production | generation of the fatty acid ester of 3-MCPD and / or 3-MCPD in a refinement | purification glyceride composition can be suppressed by the said clay treatment process, and these content can be reduced. The content of 3-MCPD and / or 3-MCPD fatty acid ester in the purified glyceride composition can be determined according to the American Oil Chemists' Society official method (AOCS Official Method Cd29c-13). Specifically, the total amount (hereinafter referred to as “True MCPD”) obtained by converting the amount of 3-MCPD and the fatty acid ester of 3-MCPD contained in the purified glyceride composition as the amount of 3-MCPD was obtained. The content of 3-MCPD was used. In the purified glyceride composition, glycidol and a fatty acid ester of glycidol are included as compounds similar to 3-MCPD and 3-MCPD fatty acid ester, but the content of 3-MCPD measured by the above method is not included. These glycidols and fatty acid esters thereof are not included.
以下、本発明の実施例に基づいてさらに詳細に説明するが、本発明はこれらの記載に何ら限定されるものではない。
下記条件にて、精製グリセリド組成物中の３−ＭＣＰＤ、及び３−ＭＣＰＤの脂肪酸エステルの生成抑制効果、及びこれらの含有量の低減可能性の検討を行った。
Hereinafter, although it demonstrates still in detail based on the Example of this invention, this invention is not limited to these description at all.
Under the following conditions, the production inhibitory effect of 3-MCPD in the purified glyceride composition and fatty acid ester of 3-MCPD, and the possibility of reducing the content thereof were examined.
（試験１）
［実施例１］
原料となるグリセリド組成物として、パーム粗油（Ｉｎｔｅｒｃｏｎｔｉｎｅｎｔａｌ Ｓｐｅｃｉａｌｔｙ Ｆａｔｓ Ｓｄｎ． Ｂｈｄ．社製）を使用した。当該パーム粗油１００ｇを９０℃にて５分間加熱し、その後リン酸３０μｌ（パーム粗油全体に対して０．０４質量％）を加え、１０分間撹拌した。撹拌後、得られた脱ガムグリセリド組成物（脱ガムパーム粗油）に、アルカリ白土（Ｎａｔｕｒａｌ Ｂｌｅａｃｈ ＳＤＮ．ＢＨＤ社製、ＮＢ１４０００、ｐＨ＝８．６）２００ｍｇ（脱ガムパーム粗油全体に対して２質量％）、及び、炭酸カリウム１０ｍｇ（脱ガムパーム粗油全体に対して０．１質量％）をさらに加え、９０℃で２０分間撹拌し、脱ガムグリセリド組成物（脱ガムパーム粗油）と白土及び炭酸カリウムの混合物を接触させた。その後得られた接触後の組成物をろ紙にてろ過し、精製されたグリセリド組成物（精製パーム油）を得た。
［比較例１］
脱ガムグリセリド組成物を、白土及び炭酸カリウムの混合物と接触させない以外は、実施例１と同様に実験を繰り返し、比較例１のグリセリド組成物（パーム油）を得た。
［比較例２〜６］
炭酸カリウムの代わりに表１に示す各種アルカリを使用した以外は、実施例と同様に実験を繰り返し、比較例２〜６のグリセリド組成物（パーム油）を得た。
(Test 1)
[Example 1]
Palm crude oil (Intercontinental Specialty Fats Sdn. Bhd.) Was used as a glyceride composition as a raw material. 100 g of the crude palm oil was heated at 90 ° C. for 5 minutes, and then 30 μl of phosphoric acid (0.04% by mass with respect to the total crude crude oil) was added and stirred for 10 minutes. After stirring, the obtained degummed glyceride composition (degummed palm crude oil) was added to 200 mg of alkaline clay (Natural Bleach SDN.BHD, NB14000, pH = 8.6) (2 mass relative to the entire degummed palm crude oil). %) And 10 mg of potassium carbonate (0.1% by mass with respect to the whole degummed palm crude oil), and further stirred at 90 ° C. for 20 minutes, degummed glyceride composition (degummed palm crude oil), white clay and carbonic acid A mixture of potassium was contacted. Thereafter, the obtained composition after contact was filtered with a filter paper to obtain a purified glyceride composition (purified palm oil).
[Comparative Example 1]
The experiment was repeated in the same manner as in Example 1 except that the degummed glyceride composition was not contacted with the mixture of clay and potassium carbonate, to obtain a glyceride composition (palm oil) of Comparative Example 1.
[Comparative Examples 2 to 6]
Except having used the various alkalis shown in Table 1 instead of potassium carbonate, the experiment was repeated in the same manner as in Examples to obtain glyceride compositions (palm oil) of Comparative Examples 2 to 6.
（白土のｐＨの測定）
蒸留水１００ｇに、実施例及び比較例において使用する白土を５ｇ加え、振り混ぜた後２５℃で１６時間インキュベートした。その後水相を取り、携帯型ｐＨメータ（機種名：ＦＥＰ−２０、メトラートレド社製）を用いて、白土のｐＨを測定した。その結果、アルカリ白土（Ｎａｔｕｒａｌ Ｂｌｅａｃｈ ＳＤＮ．ＢＨＤ社製、ＮＢ１４０００）のｐＨは８．６であり、活性白土（製品名：ＳＵＰＥＲ ＰＬＵＳ、ＴＡＩＫＯ ＣＬＡＹ ＭＡＲＫＥＴＩＮＧ ＳＤＮ．ＢＨＤ．社製）のｐＨは３．９だった。
(Measurement of pH of white clay)
5 g of white clay used in Examples and Comparative Examples was added to 100 g of distilled water, shaken and incubated at 25 ° C. for 16 hours. Thereafter, the aqueous phase was taken, and the pH of the white clay was measured using a portable pH meter (model name: FEP-20, manufactured by METTLER TOLEDO). As a result, the pH of the alkaline clay (Natural Bleach SDN. BHD, NB14000) is 8.6, and the pH of the activated clay (product name: SUPER PLUS, TAIKO PLAY MARKING SDN. BHD.) Is 3.9. was.
（３−ＭＣＰＤ生成試験）
脱臭工程で使用される温度にて加熱した場合に、実施例及び比較例のグリセリド組成物がどの程度３−ＭＣＰＤを生成するかを試験するため、３−ＭＣＰＤ生成試験を行った。具体的には、実施例及び比較例で得られた各グリセリド組成物を２ｇ計り取り、２５０℃で１時間加熱し、当該加熱前後の３−ＭＣＰＤの含有量を測定した。
精製グリセリド組成物中の３−ＭＣＰＤ及び／又は３−ＭＣＰＤの脂肪酸エステルの含有量は、上述したアメリカ油化学会公定法（ＡＯＣＳ Ｏｆｆｉｃｉａｌ Ｍｅｔｈｏｄ Ｃｄ２９ｃ−１３）に準拠して行った。
(3-MCPD generation test)
In order to test how much the glyceride compositions of Examples and Comparative Examples produce 3-MCPD when heated at the temperature used in the deodorization step, a 3-MCPD production test was performed. Specifically, 2 g of each glyceride composition obtained in Examples and Comparative Examples was weighed and heated at 250 ° C. for 1 hour, and the content of 3-MCPD before and after the heating was measured.
The content of the fatty acid ester of 3-MCPD and / or 3-MCPD in the purified glyceride composition was performed in accordance with the above-mentioned American Oil Chemistry Society official method (AOCS Official Method Cd29c-13).
具体的には、実施例及び比較例のグリセリド組成物中に含まれる３−ＭＣＰＤ及び３−ＭＣＰＤの脂肪酸エステルの量を、３−ＭＣＰＤの量として換算した総量を求め、これを３−ＭＣＰＤの含有量とした。なお、ＡＯＣＳ Ｏｆｆｉｃｉａｌ Ｍｅｔｈｏｄ Ｃｄ２９ｃ−１３で用いた、ガスクロマトグラフ質量分析装置の分析条件は次のとおりである。
（ガスクロマトグラフ質量分析装置の分析条件）
分析装置：島津製作所株式会社製、機種名：ＱＰ−２０１０
カラム：製品名：ＨＰ−５ＭＳ、Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｙ社製（長さ３０ｍ、径０．２５ｍｍ）
カラム温度：６０℃（１分）〜１２０℃（昇温速度１０℃／分）〜１９０℃（昇温速度６℃／分）〜２８０℃（昇温速度２０℃／分）
検出器：ＭＳ（ＥＩ，ＳＩＭモード）
スプリットレス：１μＬ注入
キャリアガス：Ｈｅ
Specifically, the amount of 3-MCPD and the fatty acid ester of 3-MCPD contained in the glyceride compositions of Examples and Comparative Examples was calculated as the amount of 3-MCPD, and this was determined as the amount of 3-MCPD. It was set as content. In addition, the analysis conditions of the gas chromatograph mass spectrometer used by AOCS Official Method Cd29c-13 are as follows.
(Analysis conditions of gas chromatograph mass spectrometer)
Analytical device: manufactured by Shimadzu Corporation, model name: QP-2010
Column: Product name: HP-5MS, manufactured by Agilent Technology (length 30 m, diameter 0.25 mm)
Column temperature: 60 ° C. (1 minute) to 120 ° C. (temperature increase rate 10 ° C./min) to 190 ° C. (temperature increase rate 6 ° C./min) to 280 ° C. (temperature increase rate 20 ° C./min)
Detector: MS (EI, SIM mode)
Splitless: 1 μL injection Carrier gas: He
上記実施例１及び比較例１〜６の試験結果を表１に示す。以下、表中の「３−ＭＣＰＤ換算量」は、遊離３−ＭＣＰＤ量に換算された、精製グリセリド組成物中の３−ＭＣＰＤ、及び３−ＭＣＰＤの脂肪酸エステルの総量を示す。 The test results of Example 1 and Comparative Examples 1 to 6 are shown in Table 1. Hereinafter, “3-MCPD conversion amount” in the table indicates the total amount of 3-MCPD in the purified glyceride composition and the fatty acid ester of 3-MCPD converted to the amount of free 3-MCPD.
表１
上記表１に示したように、白土と炭酸カリウムとの混合物を使用した場合(実施例１)、炭酸ナトリウム等の他のアルカリを使用した場合に比べて３−ＭＣＰＤの生成を大幅に低減することができることがわかった。
（試験２）
［実施例２〜１３］
リン酸３０μｌの代わりに、１０％リン酸水溶液を０．５ｍｌ（パーム粗油全体に対して０．０５質量％）又は１０％クエン酸水溶液を０．５ｍｌ（パーム粗油全体に対して０．０５質量％）使用した以外は、実施例１と同様にして、脱ガムグリセリド組成物（脱ガムパーム粗油）を得た。得られた脱ガムグリセリド組成物（脱ガムパーム粗油）を１０ｇ計り取り、アルカリ白土（Ｎａｔｕｒａｌ Ｂｌｅａｃｈ ＳＤＮ．ＢＨＤ社製、ＮＢ１４０００）２００ｍｇ（脱ガムパーム粗油全体に対して２質量％）又は活性白土（ＴＡＩＫＯ ＣＬＡＹ ＭＡＲＫＥＴＩＮＧ ＳＤＮ．ＢＨＤ．社製、ＳＵＰＥＲ ＰＬＵＳ、ｐＨ＝３．９）２００ｍｇ（脱ガムパーム粗油全体に対して２質量％）、及び、炭酸カリウムを１０ｍｇ（脱ガムパーム粗油全体に対して０．１質量％）、３０ｍｇ（脱ガムパーム粗油全体に対して０．３質量％）又は５０ｍｇ（脱ガムパーム粗油全体に対して０．５質量％）さらに加え、９０℃で２０分間撹拌し、脱ガムグリセリド組成物（脱ガムパーム粗油）と白土及び炭酸カリウムの混合物を接触させた。その後得られた接触後の組成物をろ紙にてろ過し、精製されたグリセリド組成物（精製パーム油）を得た。使用した白土や炭酸カリウムの含有量等、詳細は表２に示す。
As shown in Table 1 above, when a mixture of clay and potassium carbonate is used (Example 1), the production of 3-MCPD is greatly reduced compared to the case where other alkalis such as sodium carbonate are used. I found out that I could do it.
(Test 2)
[Examples 2 to 13]
Instead of 30 μl of phosphoric acid, 0.5 ml of a 10% aqueous phosphoric acid solution (0.05% by mass with respect to the whole crude palm oil) or 0.5 ml of a 10% aqueous citric acid solution (0. 05 mass%) A degummed glyceride composition (degummed palm crude oil) was obtained in the same manner as in Example 1 except that it was used. 10 g of the resulting degummed glyceride composition (degummed palm crude oil) was weighed out and 200 mg of alkaline clay (Natural Bleach SDN. BHD, NB14000) (2% by mass relative to the total degummed palm crude oil) or activated clay ( TAIKO PLAY MARKING SDN.BHD., SUPER PLUS, pH = 3.9) 200 mg (2% by mass with respect to the whole degummed palm crude oil) and 10 mg of potassium carbonate (0 with respect to the whole degummed palm crude oil) 0.1% by mass), 30 mg (0.3% by mass with respect to the whole degummed palm crude oil) or 50 mg (0.5% by mass with respect to the entire degummed palm crude oil), and further stirred at 90 ° C. for 20 minutes. A mixture of the degummed glyceride composition (degummed palm crude oil), clay and potassium carbonate was contacted. Thereafter, the obtained composition after contact was filtered with a filter paper to obtain a purified glyceride composition (purified palm oil). Table 2 shows details of the white clay and potassium carbonate content used.
［比較例７〜１０］
アルカリを使用しない以外は、上記実施例２〜１３と同様にして精製されたグリセリド組成物（精製パーム油）を得た。なお、比較例７は実施例２〜４に対応し、比較例８は実施例５〜７に対応し、比較例９は実施例８〜１０に対応し、比較例１０は実施例１１〜１３にそれぞれ対応する。
上記３−ＭＣＰＤ生成試験及び上記ガスクロマトグラフ質量分析装置の分析条件に基づいて、実施例２〜１３及び比較例７〜１０を試験した試験結果を表２に示す。以下、表中の「３−ＭＣＰＤ換算量」は、遊離３−ＭＣＰＤ量に換算された、精製グリセリド組成物中の３−ＭＣＰＤ、及び３−ＭＣＰＤの脂肪酸エステルの総量を示す。
[Comparative Examples 7 to 10]
A glyceride composition (purified palm oil) purified in the same manner as in Examples 2 to 13 except that no alkali was used was obtained. Comparative Example 7 corresponds to Examples 2 to 4, Comparative Example 8 corresponds to Examples 5 to 7, Comparative Example 9 corresponds to Examples 8 to 10, and Comparative Example 10 corresponds to Examples 11 to 13. Correspond to each.
Table 2 shows test results obtained by testing Examples 2 to 13 and Comparative Examples 7 to 10 based on the 3-MCPD generation test and the analysis conditions of the gas chromatograph mass spectrometer. Hereinafter, “3-MCPD conversion amount” in the table indicates the total amount of 3-MCPD in the purified glyceride composition and the fatty acid ester of 3-MCPD converted to the amount of free 3-MCPD.
表２
表２に示すように、特定量の炭酸カリウムを使用することにより、３−ＭＣＰＤの生成を大幅に低減することができることがわかった。特に、０．３〜０．５質量％の範囲で炭酸カリウムを使用すると、好適に３−ＭＣＰＤの生成を低減できることがわかった。 As shown in Table 2, it was found that the production of 3-MCPD can be greatly reduced by using a specific amount of potassium carbonate. In particular, it was found that the use of potassium carbonate in the range of 0.3 to 0.5% by mass can favorably reduce the production of 3-MCPD.
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| JP6008596B2 (en) * | 2011-06-15 | 2016-10-19 | 花王株式会社 | Method for producing refined fats and oils |
| JP5216942B1 (en) * | 2011-07-29 | 2013-06-19 | 日清オイリオグループ株式会社 | Purified glyceride composition and method for producing the purified glyceride composition |
| JP2014068541A (en) * | 2012-09-27 | 2014-04-21 | Chikuno Shokuhin Kogyo Kk | Manufacturing method of edible oil |
| JP6441072B2 (en) * | 2014-12-26 | 2018-12-19 | ミヨシ油脂株式会社 | Method for reducing chloropropanols in edible fats and oils |
| CN106635250A (en) * | 2016-12-08 | 2017-05-10 | 安徽凯奥新能源股份有限公司 | Method for preparing transformer oil from edible vegetable oil |
-
2016
- 2016-12-15 JP JP2016242873A patent/JP6857017B2/en active Active
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2017
- 2017-12-14 EP EP17880767.3A patent/EP3556833A4/en active Pending
- 2017-12-14 MY MYPI2019001692A patent/MY193155A/en unknown
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021017452A (en) * | 2019-07-17 | 2021-02-15 | 日清オイリオグループ株式会社 | Method for producing refined fat/oil |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018110637A1 (en) | 2018-06-21 |
| EP3556833A1 (en) | 2019-10-23 |
| EP3556833A4 (en) | 2020-05-20 |
| MY193155A (en) | 2022-09-26 |
| JP6857017B2 (en) | 2021-04-14 |
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